DE2256289A1 - NEW PYRIMIDINE - Google Patents

Description

The invention relates to new "compounds of the general formula

KHR

X = H, 3r

R = in the case of X = H the same alkyl radicals with 3-6 carbon atoms, which together with do not form a straight chain with the nitrogen, in the case X = Br the same alkyl '"' or cycloalkyl radicals with J-6 C-v Atoms.

The following compounds may be mentioned individually: 2,4-bis (-iso-propylamino) -5-bromo-6-diethyluracil

2 ₎ 4 ~ bis (-n-butylamino) - ^ - bromo-G-methyluracil 2,4-bis (-iso-butylamino) -5-bromo-6-methyluracil 2,4-bis (-see.-butylamino) -5-bromo-6-methyluracil 2,4-bis-cyclohexylamino-p-bromo-G-methyluracil 2,4-bis (-1,3-dimethylbutylamino) -5-brcm-6-methylur * acil 2,4- Bis (-iso-propylamino) -6-methylpyrimidine 2,4-bis (-iso-butylamino) -6-meth-tipyrimidine, 2,4-bis (-sec-butylamino) -6-methylpyrimidine 2,4-bis (-1 , 3-dimethylbutylamino) -6-methylpyrimidine

Pyrimidines or their hydrobromides of the general formula

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NHR

are made by either

1) one mole of 6-methyluracil with 1-3 moles of the corresponding Phosphoric triamide of the general structure O = P (-NHR) ,. in Presence of an amine hydrochloride 0.2-8 hours, preferably 0.5-4- hours at 130-280 ° C, preferably 160-260 ° C heated, or

2) 6-Methyluracil in a known manner to 2,4-dichloro-6-iaethylpyrimidine reacted and this then with at least 4 mol of the corresponding amine, optionally under pressure at 0 190 C reacts, and

3) the 2,4-diamino-6-methylpyrinidine formed in both cases is removed from the reaction mixture with a water-immiscible solvent, cleaned by vacuum distillation,

4) then brominated at 0 - "TSQ ⁰ C, preferably 30 - bo ° C with 0.95 -1.1 mol of 3rom per mol of pyrimidine in the presence of chlorinated hydrocarbons or lower aliphatic carboxylic acids, and

5) optionally with the addition of a strong base, the corresponding one Hydrobromide into the free 2,4-diamino-5-brcm-6-methylpyrimidine converts.

The amidation mentioned in reaction stage 1) takes place according to the following reaction scheme:

0 = P_

O = P-

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3 I.

-0 = P_

The phosphoric acid triamides required for this purpose were by reacting phosphorus oxychloride with the appropriate Amines in carbon tetrachloride at 35 ° - 40 ° C 'produced. Reaction time: 6 hours. The thereby 'precipitated hydrochloride was filtered off and. the filtrate concentrated. That as an impurity residual hydrochloride served as a catalyst.

O = P Cl ₃ + 6 HN <-—> O = P- N <+ 3 HCl · ΗΝ «

⁵ \

The start of the reaction is between 130 to 280 ° C depending on applied catalyst (amine hydrochloride) and phosphoric acid triamide. Correspondingly, the temperature maximum at the start of reflux is also different (about 280 ° C.). on the other hand the reaction time is in turn dependent on the reaction temperature and the phosphoric acid triamide used. It is mostly between 0.5 and 4 hours.

The production method of 2,4 ~ diamino-6-methylpyrimidines listed under 2) proceeds according to the following reaction scheme

0 cl

Suitable solvents for the reaction of 2,4-dichloro-6-methylpyrimidine are for example chlorinated hydrocarbons, e.g. chlorobenzene, dichlorobenzenes, water, Alcohols, optionally mixed with water, such as methanol, Ethanol, butanol, ... propanol, pentanol, hexanol, heptanol, Octanol, glycol, glycerine, propanediol, butanediol, hydrocarbons, for example toluene, xylene, phenols. '

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The amidation took place in two stages. The first stage already takes place at a low temperature, whereby for economic reasons usually ni <
It is strongly exothermic.

For borrowed reasons, work is usually not carried out below 0 ° C.

The amidation of the second chlorine atom is only achieved at a temperature above 90 ° C, preferably above 120 ° C. Therefore, low-boiling amines work in one Pressure vessel advantageous.

As an organic phase for the separation of the 2,4-diamino-6-methylpyrimidines on the one hand from phosphoric acid amides and phosphoric acid on the other hand from amine hydrochlorides (Level 3) are, for example, chlorinated carbon dioxide, for example carbon tetrachloride, chloroform, methylene chloride, hydrocarbons, for example benzene, Toluene, ethers, for example diethyl ether, dibutyl ether, tetrahydrofuran.

Suitable solvents for the bromination ■ (level 4) are halogenated hydrocarbons, such as carbon tetrabromo and carbon tetrachloride, Chloroform, methylene chloride and lower aliphatic carboxylic acids, for example acetic acid, propionic acid.

Suitable bases include alkali metal hydroxides, for Example sodium, potassium hydroxide, tert. Amines, for example Triethylenediamine, trimethylamine, triethylamine, tributylamine, H-nethylpyrrolidine, N-IIethylmorpholine.

The 2,4-diamino-5-bromo-6-methylpyrimidines listed in claim 1 according to the formula

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KHR

CH, - ^X

3.

where R = identical alkyl or cycloalkyl radicals with 3-6 C atoms means

or their hydrobromides are used as pesticides, in particular used as herbicides and fungicides with good success.

As far as the compounds found have herbicidal properties, they act post-emergence and have a pronounced effect Selectivity against maize, partly against other useful crops. grasses like barley.

The active ingredients can usually be added to emulsion concentrates, Wettable powders or dusts.

Examples of the production of the products according to the invention:

A amidation with phosphoric acid triamides

example 1

2,4-bis (-n-butylamino) -6-methylpyrimidine

. N

0.5 mole of phosphoric acid tri-n-butylamide and 0.25 mole of 6-methyluracil were heated to 200 ° C. for 0.5 hours, then

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cooled, mixed with chloroform, washed with soda and extracted with chloroform.

After the solvent had been stripped off, it was distilled in a high vacuum through a 15 cm column.

Yield: 23.3 g of 2,4-bis (-n-butylamino) - 6-methylpyrimidine ^Sp 0.5-0.3 mm Hg ^{: 1} 34-157 ° C

The structure was confirmed by NMR spectroscopy.

Example 2

2 _{tons of} 4-bis (-iso-butylamino) -6-methylpyrimidine

157 g contaminated with Isobutylaminhydrochlorid phosphoric acid tri- (iso-butylamide) were heated with 4-7 »5 S (0.375 mol) of 6-Metbyluracil to reflux (215 ⁰ C). The temperature fell ^{to 180 °} C. in the course of the reaction and was held for 1 hour. After cooling, the mixture was boiled with chloroform until it was completely dissolved, sodium carbonate solution (500 ml) was added and the organic phase was separated off and filtered.

The piltrate was dried with potassium carbonate, filtered and concentrated, and the residue was distilled in vacuo. Very strong fumes appeared from the beginning.

"- 160 ⁰ C

Yield of crude product (2,4-bis (-iso-butylamino) -6-methylpyrimidine 39 g.

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Example 3

2,4-BisC-sec-butyl amino) -6-methylpyrimidine

127.7 g contaminated with sea-butylamine hydrochloride Phosphoric acid triC-sec-butylamide) and 0.25 mol of 6-methyluracil were heated to reflux (235 ^. Temperature drop on 200 °, reaction time: 1 hour. Work-up as in Example 1

Distillate: Sp ^ ₂ _ ^^ _Hg: 1 ₅ 0 ° exploiter of crude product: 36.7 g

Example 4- . ·

2,4-BiaC-iso-propylamino) -6-methylpyrimidine

121 g of phosphoric acid tri contaminated with isopropylamine hydrochloride iso-propylamide) and 0.25 mol of 6-methyluracil.

Heated to reflux (approx. 205 °) for 1 hour and carried out analogously to Example 1

worked up.

Yield of crude product: 29 g

¹ 35 - 160 ⁰ C

^S P 0.2-0.5 mm Hg ^{: 1}

Example 5 .

2,4- Bi ^ -1,3-dimethylbutylamino) -6-methylpyrimidine

46 g of phosphoric acid tri (-1, ^ - dimethylbutylamide) contaminated with 1,3-dimethylbutylamine hydrochloride were heated to 260% with 7 g of 6-methyluraci.l (reflux). The temperature slowly decreased to 225 ° G.
Reaction time: 1 hour, work-up as in Example 1

^S P-0.2-0.5 mmHg ^: ^ ⁰ ' ¹ ^ ⁰ C

Example .6

2,4-bis-cyclo h ex ^ rlamino-e-methylpyriaidin ■

147 g of phosphoric acid contaminated with cyclohexylamine hydrochloride etricyclohexyl amide (approx. 0.3-0.4 mol) and 30 g of 6-methyl-

• -8- £ 098 2 3/1069

- B - ■

uracil were heated to 255 ^ and held at this temperature for 45 minutes. The work-up was carried out as in Example 1.
The yield of crude product: Λ-7 g

It was obtained in the form of a crystal pulp.

B Amidation of 2,4-dichloro-6-methylpyrimidine obtained from 6-methyluracil with amines

0.2 moles of 2,4-dichloro-6-methylpyrimidine were each with about 1 mol of the corresponding amine heated for several hours (see Table 1). In the case of low-boiling amines, the Implementation carried out in a pressure vessel. The pressure generally rose to 4 atmospheres, a maximum of 5 atmospheres. To separate the The resulting amine hydrochloride was taken up in water and treated with chloroform or carbon tetrachloride extracted. The organic phase was separated off and dried with potassium carbonate, freed from the solvent and the residue is distilled or recrystallized in vacuo (see Table 1).

The structure of all compounds was determined by NMR spectroscopy determined.

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690 I / £ 2860?

Table 1

¹ K)

cn cn

K) .00

CO

ogame Substituents on
Carbon atom 2 and 4 • pressure reaction time
hour Temperature boiling point
⁰ C mm Hg ° C / 0.4 125-130 yield 7th HHCHgCHgCHpCH, 5 atü 2 120-140 0.4 107-120 59% 8th f
2 3 2: 4 atü 3 '140-160 0.4 123-125 60% 9 NHCH (CH ₃ ) C ₂ H ₅ 5 atü / ■ 140-160 0.15 135 63% f 10 NHCH (CH,) CH ₀ CH (OH- 5> 2 3 atü .6 ' 120-140 1 * 5 2Ο5-2Ο8 70%: ,1, - 7th 140 70%

The boiling points given in Table 1 (except for Example 8) apply to the pure products and therefore do not agree well with the points given in Examples 1-6.

- ίο -

The 2,4-diamino-6-methylpyrimidines obtained in Examples 1-11 were brominated as follows:

Preparation of the hydrobromides of 2,4 - diamino - ^ - bromo-6-methyl ~ pyrimidines

0.05 WoI of the corresponding diamino-6-methylpyrimidine at room temperature in carbon tetrachloride or acetic acid (see Table 2) with 0.05 mol of bromine in the course of about 4-0 minutes added drop by drop. Any crystals that had precipitated were filtered off with suction. Otherwise the solvent was in vacuo drawn off and the residue recrystallized.

The structures of the compounds obtained were of the general Formula "

H Br

Determined by NMR spectroscopy.

Some of the melting points of the compounds changed after prolonged storage due to the splitting off of HBr. This can be different when opening the bottle (vapor formation) can be observed. This does not change the NMR spectrum.

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example

Substituents on carbon atom 2 and 4

solvent

Crystals from reaction solution

- 11 -

recrystallized the end

12th -NHCH ₂ CH ₂ CH ₂ CH ₃ Acetic acid. Yes ■■ Yes Butyl acetate 13th -NHCH ₂ CH (Cli ₃ ) ₂ acetic acid Butyl acetate 14th -NHCH (CH ") C_H_ acetic acid Butyl acetate 15th .-NHClI (CH) ₂ acetic acid acetic acid 16 -NHCH (CH ₃ ) CH ₂ CH (CH ₃ J ₂ CHCl / CCl, 1: 1 Butyl acetate 17th -NH- (H) ^CC1 4 Butyl acetate

example

yield

Analysis ( %) HN

Br

is available
as salt

with

O CD CXJ x> UJ

O CD CD

12th 109-112 72 calc .: 39.4l 6.11 l4, l4 40.34
Found: 38.47 6.51 14.36 41.9O 2 HBr 13th 172-174 67 calc .: 39.4l 6.11 I4, l4 40.34
found: 38.88 6.53 14.95 41.5O 2 HBr 14th 131-133 45 calc .: 39.4l 6.11 l4, l4 40.34
found: 39.80 6.15 l4.06 4l, l8 1 HBr \ ^15th 176-177 74 b4r.:35.9 5.95 15.2 43.45
gof .: 35.8 5.93 14.7 42.22 1 HBr ^: 16 145-151 53 ber.:45,14 7.13 12.39 35.34
found: 44.06, 6.61, 12.82, 36.7.4 1 HBr <J 17 184-185 75 calc. 45.55 6.30 12.50 35.65
found: 46.04 6.22 10.41 36.31 1 HBr
■

(Si T3

' j

■ ι ':'

- -wr-

As already mentioned, the active ingredients can usually to emulsion concentrates, wettable powders or dusts be formulated. The following formulation recipes can be used for this:

A: Emulsion concentrate

Active ingredient 10 - 50 % Gyc1oh exanon 20-60 % Xylene . 5 - 20 % Emulsifier IHS 5 - 15 % B: wettable powder Active ingredient 30-80 % Sodium Sulpho Amber dioctyl ester 2 - 3% Sodium lignosulfonate \ 0 - 4 % highly dispersed silica 0-3% kaolin 10-60 % G: dusting agent Active ingredient 5 - 25% highly dispersed silica 0-1 ° / o CaIc iumc carbonate 70 - 95 * # ■

The wetting and dispersing agents used for emulsion concentrates and wettable powders can be replaced by other suitable ones Substances e.g. GalciuiadodecylbenzenesulXonat ,, Alkylphenoläthylenoxidkondensate, Uatriumalkylnaphthalinsulfonate replaced inter alia will. Likewise, for spray powder and dust as Fillers other inert components such as talc, magnesium carbonate, montmorillonite, china clav are used will. - ·

In the case of emulsion concentrate, the active ingredient is mixed with the

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- 13 -

medium intimately mixed in a stirred tank. In the case of powder formulations, on the other hand, the dry one is used Mix by means of a hammer mill or another suitable grinding device to a grain fineness Grind under 2C / u, mixed again and finally sifted.

The herbicidal properties were tested on the following plants, sown in pots in the greenhouse, carried out:

Corn, barley, blood millet, wild oats, mustard, cornflower, sticky herb, sugar beet.

The herbicidal and fungicidal effects of the in Table 2 The substances described are summarized in Table 3.

Carrying out the herbicide tests:

14 days after emergence, the plants were treated with 6 kg / ha of active ingredient, which was formulated as an emulsion concentrate. The last time an assessment was made 28 days after the spraying.

Table 3 (Herbicid Test)

Plant connections according to example Kr. In

Table 2

12 13 14 15 16 17

Corn O O 0 0 '5 3 barley 2 2 Ό 6th 8th 6th millet 10 3 0 9 10 9 Wild oats 4th O· 0 10 9 9 mustard 9 0 0 9 3 10 Cornflower 2 3 0 10 2 10 Sticky herb 8th 2 0 6th 4th 10 turnip 10 0 0 9 0 10 ·

0 = no effectiveness 10 = plants completely destroyed

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Carrying out the? Ungicid tests:

1) grate of beans (üronyces phaseoli )

Bean plants in pots were potted with a solution that Containing 2,000 ppm of active ingredient, sprayed dripping wet. Kach For 24 hours, the beans with host spores became artificial infected and kept in the dark for 24 hours to complete the infection. After that were the beans cultivated in the greenhouse. Evaluation after 14 days.

2) Leaf spot disease on celery (Se p toria apii) Celery plants in pots were sprayed to runoff with a solution containing 2,000 ppm of active ingredient. After 24 hours, the plants were infected with a solution obtained by macerating scleria leaves infected with Septoria "in the Starmix" in distilled water. The filtrate served as an infection solution. After treatment, the plants were kept in the greenhouse under normal conditions.

3) ■ Powdery mildew (Erysiphe graminis)

Healthy barley plants in plastic trays were given a Solution containing 2,000 ppm of active ingredient sprayed to runoff. After drying, the pots were placed in the greenhouse between barley plants that were heavily infested with leek pigeons. atfellt. The infection pressure from the neighboring plants was reinforced by fans. Evaluation after 3 weeks.

Table 4 (Fungicid Test).

Disease connections according to example lir. in

Table 2 -.

12 1 ^ 14 15 16 1?

Septoria
Mildew

There were "^ efficacy indicated.

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BATH ORIGINAL

80 100 40 20th 0 30th 100 0 60 0 0 40 0 0 10 0 0 0

The active ingredients found can be used both with each other and with known herbicides, e.g. from the class of ureas, the aryloxy fatty acids, the triazines, the carbamates and Thiocarbamates, the Dinitroalkylaniline, the Acylanilide and of the dinitrophenols combined. In this way, increases in effectiveness or even better cultural compatibility can be achieved achieve. A combination with known insecticides or fungicides is also possible.

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Claims (5)

Claims R = in the case of X = H identical alkyl radicals with 3-6 C atoms which do not form a straight chain together with the nitrogen R = in the case of X = Br identical alkyl or cycloalkyl radicals with 3-6 C atoms. A process for the production of pyrimids according to claim 1 of the general formula ^ 'MR Bi or their hydrobromides, characterized in that either 1) each one mole of 6-Kethyluracil with 1-3 moles of the corresponding Phosphoric acid triamide of the general structure O = P (-KHR) -, in the presence of an amine hydrochloride 0.2-8 hours, preferably 0.5 - ° C, preferably 160 ° 280 heated to 260 ° C, or - 4 hours at ⁰ I30 2) 6-methyluracil is converted in a known manner to 2,4-dichloro-6-methylpyrimidine and this is then reacted with at least 4 mol of the corresponding amine, optionally under pressure at 0 I90 ⁰ G, and 4 0 9 8 2 3/1069 3) the 2,4-diaraine-6- ^t -nethylpyrimidiri formed in both cases is dissolved out of the reaction mixture with a solvent which is immiscible with water and purified by vacuum distillation, 4) then at 0-120 ° C, preferably 30-50 ° C with 0.95 - Ί, ¹ mole of bromine per 1 mole of pyrimidine in the presence of chlorinated hydrocarbons or lower aliphatic Carboxylic acids brominated, and 5) optionally with the addition of a strong base, the corresponding one Hydrobromide into the free S ^ -M 6-methylpyrimidine converts. 3. Use of the compounds of the general formula NHR
Br, or their hydrobromides, where R has the same meaning Claim 1 has as a pesticide. 4. Use of the compounds of the general formula NHR or their hydrobromides, where R has the same meaning Claim 1 as a herbicide. 5. Use dex * compounds of the general formula KHR or their hydrobromides, where R has the meaning according to claim 1, as fungicides. 409823/1069